JP2016194014A - Coating composition for forming substrate surface coated film and manufacturing method of blade of wind power generator - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coating composition for forming a substrate surface coated film having performance such as excellent coating property (moderate low viscosity), compatibility, impact resistance, and icing prevention property (especially a coating composition suitable for forming a coated film of a substrate surface of a blade of a wind power generator) and a manufacturing method of a blade of a wind power generator.SOLUTION: It is obtained by blending a main agent (E) obtained by mixing a fluorine-containing polymer having hydroxyl group value of 15 to 110 mgKOH/g in terms of solid component (A) and a modifier (D) containing polyether ester polyol having number average molecular weight of 500 to 3000 (B) and polyfunctional polyether polyol (C), a curing agent (F) and a solvent (G).SELECTED DRAWING: None

Description

  The present invention relates to a coating composition for forming a coating film on a substrate surface and a method for producing a blade of a wind power generator using the same.

  More specifically, the present invention is obtained by blending a main component, a curing agent, and a solvent obtained by mixing a modifier containing a polyether ester polyol and a multifunctional polyether polyol with a fluorine-containing polymer. It is a coating composition, and it is a coating composition for forming a coating on a substrate surface having excellent coating properties (appropriately low viscosity), compatibility, impact resistance, anti-icing property, etc., especially wind power generation The present invention relates to a coating composition suitable for forming a coating on a substrate surface of a machine blade.

  In addition, the present invention provides a method for manufacturing a blade of a wind power generator in which the coating composition is applied to a blade substrate surface to form a coating layer, and then a solvent contained in the coating layer is removed to form a coating film. About.

  It has been a long time since the depletion of fossil energy resources, mainly oil and coal, has become a serious concern worldwide. Therefore, development research on new energy supply systems to replace fossil energy resources is actively conducted.

  As one of them, a power generation system (wind power generation) using wind power, which is natural energy, has attracted attention. Wind power generation is becoming popular throughout the world as a clean energy supply system that has no fear of pollution such as air pollution and water pollution, and does not adversely affect living organisms and the natural environment.

  Wind generators are generally installed in locations where strong winds blow for a long time, especially on coastlines, mountain peaks, offshore, etc. where there are no high buildings or trees or other shielding in the surrounding area. Many.

  Wind power generation is a system that converts wind energy into electrical energy. As the conversion process, the kinetic energy of the wind is converted into power energy called rotation by a windmill (wind turbine), and then the rotation is accelerated by gears. Later or directly, it is transmitted to the generator and converted to electrical energy.

  As a general structure of a wind power generator, a tower body, a tower top rotating part provided on the tower body, and three blades attached to the tower top rotating part via a rotation support part (that is, “ And generators having windmill feathers ”). The tower top rotating part rotates in accordance with the direction of the wind so that the blade is directed toward the direction where the wind is blowing. As the blade, for example, a blade in which the surface of a wing-like plate piece made of wood is reinforced with fiber reinforced plastic (FRP) is used.

  Since the blades are rotated at high speed by wind power, they are strongly impacted by collisions with raindrops, garbage, insects, birds, etc., and are easily deteriorated or damaged. In winter, ice and snow adhere to the blade surface, causing a decrease in power generation efficiency.

  Furthermore, recent wind power generators have a blade rotation axis located at a high location, and the total length of the blade exceeds 40 m, so that repair work is not possible even when considering crane work at a high location. It tends to be more difficult.

  Therefore, as a method for suppressing deterioration or breakage of a blade of a wind power generator, various methods for forming a strong coating film by applying a fluorine-based paint to the surface of the blade base have been proposed.

  For example, a fluorine-containing copolymer having a number average molecular weight of 1000 to 10,000 and having a hydroxyl group and a polyester polyol having a number average molecular weight of 2000 or less as a main component, the weight ratio of the fluorine-containing copolymer / the polyester polyol. There is known a fluororesin coating composition (see Patent Document 1) having a ratio of 95/5 to 50/50.

  According to Patent Document 1, a coating film having relatively good performance such as workability, impact resistance, flexibility, and solvent resistance can be obtained, and can be used for, for example, a paint such as a pre-coated metal.

  However, since the composition of Patent Document 1 has a rigid alicyclic structure or aromatic structure in the polyester polyol as the main component, (1) the viscosity of the composition becomes too high and the handling property is inferior. (2) There were problems such as poor flexibility and poor impact resistance.

  In addition, a fluorine-containing polymer having a hydroxyl value of 110 to 250 mg KOH / g-resin, a polyester polymer having a hydroxyl value of 100 to 300 mg KOH / g-resin, a non-blocked polyisocyanate curing agent, and a solvent, A coating composition for surface coating of a blade of a wind power generator (see Patent Document 2) is known.

  According to Patent Document 2, it is possible to form a coating film on the blade surface of a wind power generator that has good weather resistance and good followability to the blade substrate and is difficult to peel off.

  However, since the composition of Patent Document 2 does not have a group capable of improving the compatibility in the polyester component, the compatibility with the polyester component and the fluorine-containing copolymer is poor when mixed with the fluorine-containing copolymer. Easy to separate, (1) poor storage stability of the composition, (2) non-uniform coating tends to occur, poor performance such as impact resistance, abrasion resistance, anti-icing properties, There were problems such as.

  As described above, the conventional coating composition still has many problems to be solved in order to be used after being exposed to a harsh environment for a long time, such as a coating film on the surface of a blade base of a wind power generator. .

JP-A-9-310041 JP 2012-026338 A

  An object of the present invention is to provide a coating composition for forming a coating film on a substrate surface (in particular, a wind power generator) having excellent coating properties (appropriately low viscosity), compatibility, impact resistance, anti-icing property and the like. It is an object of the present invention to provide a coating composition suitable for forming a coating film on the surface of a substrate of a blade, and a method for producing a blade of a wind power generator.

  As a result of diligent investigations to solve the above problems, the present inventors mixed a specific fluoroester with a modifier containing a specific polyetherester polyol and a polyfunctional polyether polyol. If it is a coating composition for forming a coating film on a substrate surface obtained by blending a main agent, a curing agent and a solvent obtained in this manner, it is particularly suitable for forming a coating film on the substrate surface of a blade of a wind power generator such as a windmill. The present invention has been completed by finding that it has excellent coating properties (appropriately low viscosity), compatibility, impact resistance, anti-icing property and the like.

  That is, the present invention relates to a fluoropolymer (A) having a hydroxyl value in terms of solid content of 15 to 110 mg KOH / g, a polyether ester polyol (B) having a number average molecular weight of 500 to 3000, and a polyfunctional polyether polyol. Base surface coating film formation obtained by blending a main agent (E) obtained by mixing a modifier (D) containing (C), a curing agent (F), and a solvent (G) The present invention relates to a paint composition.

  In the present invention, the coating composition for coating a substrate surface coating is applied to the blade substrate surface to form a coating layer, and then the solvent (G) contained in the coating layer is removed to form a coating film. The present invention relates to a method of manufacturing a blade of a wind power generator.

  The coating composition for forming a substrate surface coating film of the present invention can exhibit excellent performance such as coating property (appropriately low viscosity), compatibility, impact resistance, anti-icing property, etc. Coating material for coating on the surface of blades, exterior paints and interior paints for electronic devices such as smartphones and vehicles (vehicles, ships, airplanes, spacecrafts, etc.), protective paints for power lines and cables, or gas, liquid, It is useful for various applications such as a coating for forming a coating film on a substrate surface that comes into contact with a fluid such as a slurry. In addition, according to the method for manufacturing a blade of a wind power generator of the present invention, a strong coating film having excellent impact resistance of the coating composition that is difficult to peel off can be formed on the surface of the blade substrate.

[Coating composition for substrate surface coating formation]
The coating composition for forming a coating film on a substrate surface of the present invention includes a fluoropolymer (A) having a hydroxyl value in terms of solid content of 15 to 110 mg KOH / g (hereinafter abbreviated as a unit), and a number average molecular weight ( (Hereinafter referred to as “Mn”) 500-3000 polyether ester polyol (B) and polyfunctional polyether polyol (C) containing a modifier (D) obtained by mixing the main agent (E), It can be obtained by blending a curing agent (F) and a solvent (G).

  In the present invention, the “hydroxyl value” and “number average molecular weight” are values measured by the methods described later unless otherwise specified.

[Main agent (E)]
The main agent (E) used in the present invention is obtained by mixing a fluoropolymer (A), a modifier (D) containing a polyether ester polyol (B) and a polyfunctional polyether polyol (C). be able to.

  In the production of the main agent (E), the mass ratio [A / (B + C)] of the fluoropolymer (A) to the total mass of the polyether ester polyol (B) and the polyfunctional polyether polyol (C) is preferably Is in the range of 10/90 to 90/10, more preferably in the range of 25/75 to 75/25. When the mass ratio [A / (B + C)] is within such a range, excellent compatibility, impact resistance, wear resistance, anti-icing property, and other performances can be exhibited.

[Fluoropolymer (A)]
The fluorine-containing polymer (A) used essentially in the present invention will be described below.

  The hydroxyl value of the fluoropolymer (A) is in the range of 15 to 110, preferably in the range of 20 to 105. If the hydroxyl value of (A) is within such a range, the coating film obtained using the coating composition can exhibit excellent performance such as impact resistance and anti-icing property.

  However, when the hydroxyl value of (A) is less than 15, the wear resistance is inferior due to a decrease in coating film strength. On the other hand, when the hydroxyl value of (A) exceeds 110, the elongation of the coating film decreases, resulting in poor impact resistance.

  Moreover, Mn of the said fluoropolymer (A) becomes like this. Preferably it is the range of 1000-8000, More preferably, it is the range of 2000-7000. If the Mn of (A) is within such a range, impact resistance is improved, which is preferable.

  The fluoropolymer (A) has improved performance such as solubility in the blended solvent (G), mechanical properties (impact resistance, etc.), anti-icing property, coating properties (appropriately low viscosity), etc. In view of this, a polymer unit (a1) based on a fluoroolefin, a polymer unit (a2) based on a monomer having a hydroxyl group, and another monomer other than the monomer having a fluoroolefin or hydroxyl group (hereinafter referred to as “other unit”). A fluorine-containing polymer having a polymerized unit (a3) based on “polymer” (hereinafter referred to as “fluorinated polymer (A1)”) is preferred.

  Examples of the fluoroolefin that forms the polymer unit (a1) based on the fluoroolefin include 2 carbon atoms such as tetrafluoroethylene, chlorotrifluoroethylene, trifluoroethylene, vinylidene fluoride, hexafluoropropylene, and pentafluoropropylene. 3 fluoroolefins. Among these, tetrafluoroethylene and chlorotrifluoroethylene are preferable, and chlorotrifluoroethylene is more preferable because the alternating copolymerization with other monomers is good. 1 type may be sufficient as the polymer unit (a1) contained in a fluoropolymer (A1), and 2 or more types may be sufficient as it.

  The polymer unit (a2) based on the monomer having a hydroxyl group is preferably formed by polymerization using a monomer having a hydroxyl group.

  Examples of the monomer having a hydroxyl group include a monomer having a hydroxyl group and a polymerizable double bond. Specifically, for example, 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxy-2-methylpropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxy-2-methylbutyl vinyl ether Hydroxyalkyl vinyl ethers such as 5-hydroxypentyl vinyl ether and 6-hydroxyhexyl vinyl ether; ethylene glycol monovinyl ethers such as diethylene glycol monovinyl ether, triethylene glycol monovinyl ether and tetraethylene glycol monovinyl ether; 2-hydroxyethyl allyl ether, 4 -Hydroxyl esters such as hydroxybutyl allyl ether and glycerol monoallyl ether Kill allyl ethers; hydroxyalkyl vinyl esters such as 2-hydroxyethyl vinyl ester and 4-hydroxybutyl vinyl ester; hydroxyalkyl allyl esters such as hydroxyethyl allyl ester and hydroxybutyl allyl ester; hydroxyethyl (meth) acrylate, etc. (Meth) acrylic acid hydroxyalkyl esters and the like. Among these, hydroxyalkyl vinyl ethers are preferable as monomers having a hydroxyl group because of easy availability, and 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether are more preferable, and 2-hydroxybutyl vinyl ether is more preferable. Hydroxyethyl vinyl ether and 4-hydroxybutyl vinyl ether are more preferable.

  The polymerization unit (a2) may be formed by a method in which after polymerization is performed using a monomer having no hydroxyl group, a part of the polymerization unit of the obtained polymer is chemically converted to introduce a hydroxyl group. Good. For example, after polymerization is performed using a monomer having a functional group other than a hydroxyl group, the resulting polymer is reacted with a compound having a functional group that reacts with the functional group and a hydroxyl group, to form a polymer unit. A part (functional group) may be formed by chemical conversion. Specific examples include a method in which a diol compound is reacted with the obtained polymer after polymerization using a monomer having a carboxy group. 1 type may be sufficient as the polymer unit (a2) contained in a fluoropolymer (A1), and 2 or more types may be sufficient as it.

  The polymerized unit (a3) is a polymerized unit based on a fluoroolefin forming the polymerized unit (a1) and another monomer copolymerizable with the monomer forming the polymerized unit (a2). If the fluorinated polymer (A1) has a polymerized unit (a3), the solubility in the solvent (G) becomes better, which is preferable.

  Examples of the other monomers include vinyl ethers, allyl ethers, isopropenyl ethers, carboxylic acid vinyl esters, carboxylic acid allyl esters, carboxylic acid isopropenyl esters, methallyl ethers, and carboxylic acid methallyl esters. , Α-olefins, (meth) acrylic acid esters and the like.

  Examples of the vinyl ethers include alkyl vinyl ethers such as ethyl vinyl ether, butyl vinyl ether, cyclohexyl vinyl ether, fluoroalkyl vinyl ether, and perfluoro (alkyl vinyl ether).

  Examples of the allyl ethers include alkyl allyl ethers such as ethyl allyl ether and cyclohexyl allyl ether.

  Examples of the isopropenyl ethers include alkyl isopropenyl ethers such as methyl isopropenyl ether.

  Examples of the carboxylic acid vinyl esters include Veova 10 (trademark, manufactured by Shell Chemical Co., Ltd.), which is a fatty acid vinyl ester having a branched alkyl group, vinyl butyrate, vinyl acetate, vinyl pivalate, vinyl versatate, and the like. Examples include fatty acid vinyl esters.

  Examples of the carboxylic acid allyl esters include fatty acid allyl esters such as allyl propionate and allyl acetate.

  Examples of the α-olefins include ethylene, propylene, isobutylene and the like.

  Examples of the (meth) acrylic acid ester include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid butyl ester and the like.

  As the other monomer, vinyl ethers, carboxylic acid vinyl esters, allyl ethers, and carboxylic acid allyl esters are preferable from the viewpoint of excellent copolymerizability with a fluoroolefin, and a linear chain having 1 to 10 carbon atoms. Alkyl vinyl ethers and fatty acid vinyl esters having a linear, branched or alicyclic alkyl group are more preferred. The polymerization unit (a3) contained in the fluoropolymer (A1) may be one type or two or more types.

  The ratio of the number of moles of polymerized units (a1) to the total number of moles of all polymerized units constituting the fluoropolymer (A1) is preferably 30 to 70 mol%, more preferably 40 to 60 mol%. is there. If the ratio of the polymerized unit (a1) is within such a range, the weather resistance of the coating film, the solubility of the fluoropolymer (A1) in the solvent (G), and the solubility in the modifier (D) are sufficient. Since it improves, it is preferable.

  The ratio of the number of moles of polymerized units (a2) to the total number of moles of all polymerized units constituting the fluoropolymer (A1) is preferably 1 to 50 mol%, more preferably 3 to 40 mol%. is there. If the ratio of the polymerization unit (a2) is within such a range, the adhesion of the coating film to the blade substrate and the mechanical properties (impact resistance, etc.) are improved, which is preferable.

  The ratio of the number of moles of polymerized units (a3) to the total number of moles of all polymerized units constituting the fluoropolymer (A1) is preferably 10 to 60 mol%, more preferably 20 to 50 mol%. is there. If the ratio of the polymerized unit (a3) is within such a range, the solubility of the fluoropolymer (A1) in the solvent (G), the solubility in the modifier (D), and the adhesion to the blade surface substrate This is preferable because the property is improved.

  As the fluoropolymer (A), a fluoropolymer having a hydroxyl group other than the fluoropolymer (A1) may be used. For example, you may use the fluoropolymer which has a polymerization unit (a1) and a polymerization unit (a2), and does not have a polymerization unit (a3). The fluoropolymer (A) used in the present invention may be used alone or in combination of two or more.

  The mass ratio [A / (B + C)] of the fluoropolymer (A) to the mass sum of the polyether ester polyol (B) and the polyfunctional polyether polyol (C) is preferably 10/90 to 90 /. It is the range of 10, More preferably, it is the range of 25 / 75-75 / 25. When the mass ratio [A / (B + C)] is within such a range, excellent compatibility, impact resistance, wear resistance, anti-icing property, and other performances can be exhibited.

  The content of the fluoropolymer (A) in the coating composition for forming a coating film on the substrate surface is preferably in the range of 10 to 90% by mass, more preferably in the range of 25 to 85% by mass. When the content of the (A) is within such a range, the performance of the coating film such as weather resistance, anti-icing property, adhesion to the substrate surface, and impact resistance can be further improved.

  The fluoropolymer (A) used in the present invention may be a synthetic product or a commercial product. Commercially available products include, for example, “Zeffle GK-570” (trademark, manufactured by Daikin Corporation, hydroxyl value 55 to 65, butyl acetate solution having a nonvolatile content of 65% by mass), “Fluonate WZQ-660” (DIC stock) And a xylene solution having a hydroxyl value of 91 to 103 and a nonvolatile content of 65% by weight).

[Polyether ester polyol (B)]
Next, the polyether ester polyol (B) used essentially in the present invention will be described below.

  In the coating composition for forming a substrate surface coating film of the present invention, a modifier (D) usually containing a polyether ester polyol (B) and a polyfunctional polyether polyol (C) in the fluoropolymer (A). ) Is mixed to prepare the main agent (E).

  The polyether ester polyol (B) forms a cross-linking bond with the fluorine-containing polymer (A) and the polyfunctional polyether polyol (C) via a curing agent (F) described later, thereby further improving the machine. Strength (impact resistance, etc.) can be expressed.

  The hydroxyl value of the polyether ester polyol (B) is preferably in the range of 50 to 250, more preferably in the range of 90 to 220. If the hydroxyl value of the (B) is within such a range, bleed out from the resulting coating film (a phenomenon in which white powder is sprayed from the coating film surface or the surface is sticky) and gelation can be suppressed. Performances such as contamination resistance and compatibility with the fluoropolymer (A) can be further improved.

  Mn of the polyether ester polyol (B) is preferably in the range of 500 to 3000, more preferably in the range of 500 to 1500. If it is the range which requires Mn of said (B), while being able to improve the mechanical strength (impact resistance etc.) of a coating film more, gelatinization can be suppressed. Moreover, since the usage-amount of the solvent (G) of a coating composition can be reduced, removal and collection | recovery of a solvent can be shortened, and while being able to form a coating film easily, it can also contribute to environmental load reduction.

  The polyether ester polyol (B) used in the present invention is a dicarboxylic acid or a reactive derivative thereof [eg, acid anhydride, lower alkyl ester (alkyl ester having 1 to 4 carbon atoms such as methyl ester, ethyl ester, etc.), Acid halide (acid chloride, etc.)] and a polymer having a hydroxyl group obtained by reacting with a diol.

  Examples of the dicarboxylic acid include aliphatic dicarboxylic acids (eg, succinic acid, adipic acid, sebacic acid, glutaric acid, azelaic acid, maleic acid, fumaric acid, etc.) or alicyclic dicarboxylic acids (eg, 1,2-cyclohexane). Dicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, etc.] or aromatic dicarboxylic acid [for example, o-phthalate Acid, m-phthalic acid, p-phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, etc.]. Among these, aliphatic dicarboxylic acids are preferable because they can exhibit excellent impact resistance. These may be used alone or in combination of two or more.

  Examples of the diol include dipropylene glycol and tripropylene glycol. Among these, dipropylene glycol is preferable because of excellent compatibility with the fluoropolymer (A). These may be used alone or in combination of two or more.

  In addition to the diol, other diols may be used in combination as long as the object of the present invention is not impaired.

  Examples of the other diol include aliphatic diols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, propylene glycol, neopentyl glycol. 3-methyl-1,5-pentanediol, 1,9-nonanediol, 2,2-diethyl-1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3- Butanediol, etc.], or alicyclic diols (eg, 1,4-bis (hydroxymethyl) cyclohexane, 2,2-bis (4-hydroxycyclohexyl) propane, etc.), or aromatic diols (eg, m-xylylene) Glycol, p-xylylene glycol, bisphenols (for example, bisphenol Alkylene oxide adducts (preferably having a molecular weight of less than 500), alkylene oxide adducts of dihydroxynaphthalene (preferably having a molecular weight of less than 500), bis (2-hydroxyethyl) terephthalate Etc.]. These may be used alone or in combination of two or more. Of these, aliphatic diols are preferred.

  In addition to the dicarboxylic acid (or its reactive derivative) and the diol, the polyether ester polyol (B) includes a compound having a carboxy group and a hydroxyl group in one molecule, or a hydroxyl group and a carboxyl group in the same molecule. A cyclic ester (for example, γ-butyrolactone, δ-valerolactone, ε-caprolactone, etc.) produced by dehydration condensation may be used as necessary.

  The polyether ester polyol (B) may have a functional group other than a hydroxyl group.

  As the other functional group, a carboxyl group, an amino group, an acetoacetyl group, and an epoxy group are preferable from the viewpoint of improving the weather resistance, mechanical properties, oil resistance, curing reactivity and the like of the coating film, and the carboxyl group is preferable. More preferred.

  The method for introducing the functional group is not particularly limited as long as a known method may be adopted. For example, (Method 1) a method of copolymerizing the functional group and a monomer having a polymerizable double bond, Alternatively, (Method 2) a method in which the hydroxyl group in (B) is reacted with a compound having a functional group that reacts with the hydroxyl group together with the functional group, and the like.

  The carboxyl group can be introduced into the (B) by polymerization using a polyvalent carboxylic acid in combination. The introduction of an amino group, an acetoacetyl group, or an epoxy group is, for example, a functional group that reacts with a hydroxyl group or a carboxy group, and an amino group, an acetoacetyl group, or an epoxy group during or after the production of (B). It can introduce | transduce by making the compound which has at least one of these react.

  The polyether ester polyol (B) may be used alone or in combination of two or more.

  In the coating composition for forming a substrate surface coating film of the present invention, the content of the polyether ester polyol (B) is preferably in the range of 10 to 80% by mass. If the content of (B) is in such a range, excellent compatibility (melting stability), impact resistance, and coating properties (appropriately low viscosity) can be expressed, and the flexibility of the coating film and the substrate Performances such as follow-up performance, adhesion, and anti-icing properties can be exhibited.

[Multifunctional polyether polyol (C)]
Next, the polyfunctional polyether polyol (C) used essentially in the present invention will be described below.

  The hydroxyl value of the polyfunctional polyether polyol (C) is such that the bleed out from the coating film is suppressed, the gelation is suppressed, the stain resistance, the fluorine-containing polymer (A) and the polyether ester polyol (B). From the viewpoint of improving compatibility, the range is preferably 10 to 60.

  Moreover, Mn of the said polyfunctional polyether polyol (C) becomes like this. Preferably it is the range of 200-3000, More preferably, it is the range of 200-1000. If it is the range which requires Mn of said (C), while the mechanical strength (impact resistance etc.) of a coating film improves more, suppression of bleed-out and gelatinization can be performed easily. Moreover, since the usage-amount of the solvent (G) in the target coating composition can be reduced, a coating film can be formed easily and it can contribute to an environmental load reduction effectively.

  As the polyfunctional polyether polyol (C) used in the present invention, for example, polyether such as polypropylene glycol (PPG) and polytetramethylene glycol (PTMG), glycerin, sorbitol, ethylenediamine and the like are obtained as initiators. And propylene oxide adducts and butylene oxide adducts. Said (C) may be used alone or in combination of two or more.

  The polyfunctional polyether polyol (C) may be a commercially available product. For example, Exenol 385SO (trademark: manufactured by Asahi Glass Co., Ltd., propylene oxide adduct of sorbitol, functional group number 6, hydroxyl value 385, molecular weight 500), Exenol 430 (Trademark: manufactured by Asahi Glass Co., Ltd., propylene oxide adduct of glycerin, functional group number 3, hydroxyl value 400, molecular weight 430), PTMG650 (trademark; manufactured by Mitsubishi Chemical Corporation, polytetramethylene glycol, functional group number 2, hydroxyl value 173, Molecular weight 650), Exenol 500ED (trademark; manufactured by Asahi Glass Co., Ltd., propylene oxide adduct of ethylenediamine, functional group number 4, hydroxyl value 500, molecular weight 450).

  The polyfunctional polyether polyol (C) may have another functional group together with the hydroxyl group.

  Any other functional group may be used as long as it does not impair the object of the present invention. Among them, mechanical characteristics (impact resistance, etc.), curing reactivity, coating weather resistance, oil resistance From the viewpoint of improving performance such as property, a carboxyl group, an amino group, an acetoacetyl group, and an epoxy group are preferable, and a carboxyl group is more preferable.

  The method for introducing these functional groups is not particularly limited as long as a known method may be adopted. For example, (Method 1) a method of copolymerizing these functional groups and a monomer having a polymerizable double bond. Or (Method 2) A method in which a hydroxyl group in the bifunctional polyether ester (B) is reacted with a compound having a functional group that reacts with the hydroxyl group together with these functional groups.

  The carboxyl group can be introduced into the polyether ester polyol (B) by a polymerization reaction using a polyvalent carboxylic acid or a reactive derivative thereof in combination. The introduction of other functional groups such as an amino group, an acetoacetyl group, and an epoxy group may be performed by, for example, a functional group that reacts with a hydroxyl group or a carboxyl group during or after the production of (B), an amino group, or an acetoacetyl group. It can introduce | transduce by making the compound which has other functional groups, such as a group and an epoxy group, react.

  In the present invention, by using the polyfunctional polyether polyol (C) as a modifier (D) together with the polyether ester polyol (B), excellent compatibility (melting stability) of the coating composition is obtained. In addition to exhibiting coating properties (appropriately low viscosity), performances such as flexibility of the formed coating film, impact resistance, and followability to the blade substrate surface can be significantly improved.

  When the coating composition for forming a coating film on a substrate surface of the present invention is used, for example, for coating a substrate surface of a blade of a wind power generator, even if the blade substrate of the wind power generator rotates at a high speed and the blade substrate is greatly bent. A coating film that is difficult to peel off can be formed.

  In addition, the coating composition for forming a coating film on a substrate surface of the present invention can form a coating film rich in flexibility and durability. For example, when the blade rotates at high speed, for example, raindrops, ice and snow, garbage, insects, birds Even if the collision speed is high, the impact can be absorbed and alleviated, so that there is an advantage that the coating film is hardly damaged.

  However, the main component in which the modifier containing only the polyether ester polyol (B) is blended with the fluorine-containing polymer (A), which does not contain the polyfunctional polyether polyol (C), is formed using the coating composition. Although the flexibility of the coated film is slightly improved, it is not practical because of poor performance such as surface hardness and stain resistance.

  The resin composition for forming a substrate surface coating film of the present invention comprises a modifier (A) containing a specific polyetherester polyol (B) and a polyfunctional polyether polyol (C) in a specific fluoropolymer (A). The main agent (E) obtained by mixing D) is used to form a crosslink through the curing agent (F), so that coating properties (appropriately low viscosity), compatibility, impact resistance, ice Unprecedented superior performance such as anti-wearing properties can be expressed.

  In the present invention, the fluoropolymer (A), the polyether ester polyol (B), and the polyfunctional polyether polyol (C) are crosslinked by the curing agent (F) to form a strong network structure. Since it forms, bleed-out from the coating film is suppressed, and a stable and excellent effect can be maintained over a long period of time.

  In this invention, the said polyfunctional type polyether polyol (C) is 10-600 mass parts with respect to a total of 100 mass parts of the said polyetherester polyol (B) and polyfunctional type polyether polyol (C). It is preferable to contain. By using the above (C) in such a range, the compatibility (melting stability) and coating property (appropriately low viscosity) of the coating composition can be expressed, and the flexibility and resistance of the coating film to be formed are improved. Performances such as impact and followability to the blade base surface can be significantly improved.

  In the coating composition for forming a coating film on a substrate surface of the present invention, the content of the polyfunctional polyether polyol (C) is preferably in the range of 5 to 60% by mass with respect to the nonvolatile content in the main agent. If the content of (C) is in such a range, excellent compatibility (melting stability), impact resistance, and coating properties (low viscosity) can be expressed, and the flexibility of the formed coating film is improved. In addition, excellent performance such as followability to the blade substrate surface, adhesion, and weather resistance can be obtained.

[Curing agent (F)]
As the curing agent (E) used in the present invention, known ones can be used. Among them, a polyisocyanate curing agent that is not blocked (hereinafter referred to as “non-blocked polyisocyanate curing agent”). , "Unblocked polyisocyanate").

  The “unblocked polyisocyanate” referred to in the present invention is a curing agent having two or more isocyanate groups not protected by a protecting group.

  The curing agent (F) is a fluorine-containing polymer (A) contained in the main agent (E), and a modifier (D) containing a polyether ester polyol (B) and a polyfunctional polyether polyol (C). ) To form a strong network structure.

  The reaction conditions (temperature, pressure, time, atmosphere, etc.) during the crosslinking reaction are not particularly limited. In terms of temperature, it is usually preferably 100 ° C. or lower.

  The polyisocyanate curing agent is a compound having two or more isocyanate groups in one molecule, and the number of isocyanate groups in one molecule is preferably 2 to 4, more preferably 2 or 3. It is a piece.

  Examples of the polyisocyanate curing agent include aliphatic polyisocyanates such as ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, hexamethylene triisocyanate, and lysine diisocyanate; or isophorone diisocyanate, dicyclohexylmethane diisocyanate, diisocyanate methylcyclohexane. And non-yellowing aromatic polyisocyanates such as m-xylene diisocyanate and p-xylene diisocyanate. These may be used alone or in combination of two or more.

  As the curing agent (F), a modified product of the polyisocyanate can also be used. Examples of the modified polyisocyanate include urethane-modified products, urea-modified products, isocyanurate-modified products, burette-modified products, allophanate-modified products, and carbodiimide-modified products. Among these, an isocyanurate modified body, a burette modified body, and a urethane modified body are preferable, and an isocyanurate modified body and a burette modified body are more preferable. These may be used alone or in combination of two or more.

  Among the above-mentioned curing agents (F), non-yellowing polyvalent isocyanate compounds such as hexamethylene diisocyanate and isophorone diisocyanate, and their isocyanurate-modified and burette-modified products are preferable.

  The coating composition for forming a coating film on a substrate surface of the present invention is preferably blended immediately before the coating composition is applied to a substrate surface such as a blade.

  The compounding quantity of the hardening | curing agent (F) in the coating composition for base-surface coating-film formation of this invention is a fluorine-containing polymer (A), polyether ester polyol (B), and polyfunctional type polyether polyol (C). It is preferable to blend the (F) so that the isocyanate group in the curing agent (F) is 0.8 to 1.2 mol per 1 mol of the hydroxyl group. If the blending amount of the (F) is within such a range, the (A) to (C) are sufficiently cross-linked to leave no unreacted curing agent and improve the performance of the resulting coating film. ,preferable.

  The blending amount of the curing agent (F) is preferably based on 100 parts by mass in total of the fluoropolymer (A), the polyether ester polyol (B), and the polyfunctional polyether polyol (C). Is in the range of 40-120 parts by weight. If the blending amount of the (F) is within such a range, the (A) to (C) are sufficiently cross-linked to leave no unreacted curing agent and improve the performance of the resulting coating film. ,preferable.

[Solvent (G)]
As the solvent (G) used in the present invention, any solvent can be used as long as it can uniformly dissolve or disperse the main agent (E) and the curing agent (F) and does not adversely affect the reaction and performance. .

  Further, the solvent (G) may be used in any production stage. For example, it may be used as a reaction raw material or additive solvent such as the main agent (E) or the curing agent (F), and may be used as a diluent for the resulting coating composition, and is not particularly limited.

  Examples of the solvent (G) include ketones, esters, carbonates, ethers, and aromatic hydrocarbons. Specifically, methyl ethyl ketone, 2-pentanone, methyl isopropyl ketone, 2-hexanone, methyl isobutyl ketone, pinacholine, 2-heptanone, 4-heptanone, diisopyrrole ketone, isoamyl methyl ketone, 2-octanone, 2-nonanone Diisobutyl ketone, ethyl formate, propyl formate, isopropyl formate, butyl formate, isobutyl formate, sec-butyl formate, t-butyl formate, amyl formate, isoamyl formate, hexyl formate, cyclohexyl formate, heptyl formate, octyl formate, 2-formate 2- Ethylhexyl, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, t-butyl acetate, amyl acetate, isoamyl acetate, hexyl acetate, cyclohexyl acetate, hep acetate Octyl acetate, 2-ethylhexyl acetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, butyl propionate, isobutyl propionate, sec-butyl propionate, t-butyl propionate, amyl propionate, Isoamyl propionate, hexyl propionate, cyclohexyl propionate, heptyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, isopropyl butyrate, butyl butyrate, isobutyl butyrate, sec-butyl butyrate, t-butyl butyrate, amyl butyrate, isoamyl butyrate, Hexyl butyrate, cyclohexyl butyrate, methyl isobutyrate, ethyl isobutyrate, propyl isobutyrate, isopropyl isobutyrate, butyl isobutyrate, isobutyl isobutyrate, sec-butyl isobutyrate, isobutyric acid -Butyl, amyl isobutyrate, isoamyl isobutyrate, hexyl isobutyrate, cyclohexyl isobutyrate, methyl valerate, ethyl valerate, propyl valerate, isopropyl valerate, butyl valerate, isobutyl valerate, sec-butyl valerate, T-butyl herbate, amyl valerate, methyl isovalerate, ethyl isovalerate, propyl isovalerate, isopropyl isovalerate, butyl isovalerate, isobutyl isovalerate, sec-butyl isovalerate, isovaleric t -Butyl, amyl isovalerate, methyl hexanoate, ethyl hexanoate, propyl hexanoate, isopropyl hexanoate, butyl hexanoate, isobutyl hexanoate, sec-butyl hexanoate, t-butyl hexanoate, methyl heptanoate, heptanoic acid Ethyl, propyl heptanoate, isopropyl heptanoate Pyl, methyl octanoate, ethyl octanoate, methyl nonanoate, methyl cyclohexanecarboxylate, ethyl cyclohexanecarboxylate, propyl cyclohexanecarboxylate, isopropyl cyclohexane carboxylate, 2-propoxyethyl acetate, 2-butoxyethyl acetate, 2-pentyl acetate Oxyethyl, 2-hexyloxyethyl acetate, 1-ethoxy-2-acetoxypropane, 1-propoxy-2-acetoxypropane, 1-butoxy-2-acetoxypropane, 1-pentyloxy-2-acetoxypropane, acetic acid 3- Methoxybutyl, 3-ethoxybutyl acetate, 3-propoxybutyl acetate, 3-butoxybutyl acetate, 3-methoxy-3-methylbutyl acetate, 3-ethoxy-3-methylbutyl acetate, 3-propoxy-3-methylbutyl acetate , 4-methoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 4-butoxybutyl acetate, ethyl methyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, tetrahydrofuran, propylene glycol monomethyl ether, xylene, toluene, etc. Is mentioned. These solvents may be used alone or in combination of two or more.

  The amount of the solvent (G) in the coating composition is preferably in the range of 60 to 99.95% by mass, more preferably in the range of 70 to 99.95% by mass. If the blending amount of the (G) is within such a range, the viscosity of the coating composition becomes moderate, and the coating workability is excellent, and the coating film can be formed by removing and collecting the solvent (G) after coating. Since it becomes easy, it is preferable.

[Other ingredients]
Various catalysts and additives may be blended in the coating composition for forming a coating film on a substrate surface of the present invention depending on the purpose.

  A curing catalyst may be added to the coating composition for forming a substrate surface coating film of the present invention. By containing a curing catalyst, the crosslinking reaction can be promoted at a low temperature and in a short time, which is preferable.

  A known curing catalyst can be used as the curing catalyst, and examples thereof include dibutyltin dilaurate and dioctyltin dilaurate. The curing catalyst may be used alone or in combination of two or more.

  Although the usage-amount of the said curing catalyst is not restrict | limited in particular, Usually, it is the range of 0.001-10 mass parts with respect to 100 mass parts of hardening | curing agents (E), More preferably, it is 0.001-5 masses. Part range. If the amount of the curing catalyst used is within such a range, the effect of the curing catalyst can be appropriately obtained, and the possibility that the curing catalyst may remain and adversely affect the coating film and cause adverse effects such as reduced water resistance. .

  The coating composition for forming a coating film on a substrate surface of the present invention can contain a pigment for the purpose of improving performances such as rust prevention, coloring and reinforcement.

  Examples of the pigment include rust preventive pigments, colored pigments, extender pigments, and the like.

  The rust preventive pigment is a pigment for preventing corrosion or alteration of the surface of a substrate such as a blade. Lead-free rust preventive pigments are preferred because of their low environmental impact. Examples of the lead-free rust preventive pigment include cyanamide zinc, zinc oxide, zinc phosphate, calcium magnesium phosphate, zinc molybdate, barium borate, and calcium cyanamide zinc.

  The colored pigment is a pigment for coloring the coating film. Examples of the color pigment include titanium oxide, carbon black, and iron oxide. In the case of using titanium oxide, it is preferable that the pigment surface is treated for suppressing the photocatalytic action for the purpose of further improving the weather resistance of the coating film. Examples of commercially available colored pigments include D918 (trademark, manufactured by Sakai Chemical Co., Ltd.), PFC105 (trademark, manufactured by Ishihara Sangyo Co., Ltd.), and the like.

The extender pigment is a pigment for improving the hardness of the coating film and increasing the thickness. Examples of extender pigments include talc, barium sulfate, mica, calcium carbonate, and the like.
As the pigment component, titanium oxide is particularly preferable from the viewpoint of excellent weather resistance.

  When the pigment is contained in the coating composition for forming a coating film on a substrate surface of the present invention, the content of the pigment in the coating composition is 50 to 100 parts by mass with respect to 100 parts by mass of solids other than the pigment in the coating composition. 500 parts by mass is preferable, and 100 to 400 parts by mass is more preferable. If the content of the pigment is within this range, the coating will not be damaged even if it is subjected to strong impacts such as raindrops, snow, snow, garbage, insects, birds, etc. without impairing the function of the pigment. This is preferable because the properties are further improved.

  Moreover, the coating composition for base-surface coating-film formation of this invention may mix | blend a well-known additive suitably in the range which does not inhibit the objective of this invention.

  Examples of the additive include a silane coupling agent for improving the adhesion of a coating film; a light stabilizer such as a hindered amine light stabilizer; a benzophenone compound, a benzotriazole compound, a triazine compound, and a cyanoacrylate compound. Organic UV absorbers such as: Inorganic UV absorbers such as zinc oxide and cerium oxide; Matting agents such as ultrafine synthetic silica; Surfactants (cationic, anionic, nonionic, amphoteric); Leveling agents A filler (inorganic filler, organic filler); a thermal stabilizer; a thickener; a dispersant; an antistatic agent;

  When an antistatic agent is added to the coating composition for forming a coating film on a substrate surface of the present invention, a conductive coating film can be formed on the blade surface, and damage to the blade of a wind power generator due to lightning strike can be suppressed.

Examples of the antistatic agent include a cation component such as Li ⁺ , Na ⁺ , K ⁺ , Cl ⁻ , Br ⁻ , I ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , SCN ⁻ , ClO ₄ ⁻ , CF ₃ SO ₃ ^−. , (CF ₃ SO ₂ ) ₂ N ⁻ , alkali metal salts composed of anionic components such as (CF ₃ SO ₂ ) ₃ C ⁻ ; antimony-doped tin dioxide, aluminum-doped zinc oxide, gallium-doped zinc oxide, gallium-doped oxidation Examples thereof include metal oxides doped with non-oxide metals such as indium and antimony-doped titanium oxide.

  In addition, the coating composition for forming a substrate surface coating film of the present invention contains an acrylic compound, an epoxy compound, various polymers other than the fluoropolymer (A), etc., as long as the object of the present invention is not impaired. May be.

  When the coating composition for forming a coating film on a substrate surface of the present invention is used, the coating film for protecting the substrate surface (particularly, the coating film for protecting the blade substrate surface of a wind power generator) has weather resistance and followability to the substrate. It is possible to form a coating film that is highly resistant to peeling.

  In addition, since the coating film formed by the coating composition for forming a coating film on a substrate surface of the present invention has excellent flexibility, it can be subjected to strong impacts such as raindrops, ice and snow, garbage, insects and birds. The coating film is hardly damaged and has excellent performance such as weather resistance and stain resistance.

  Since the coating composition for forming a coating film on a substrate surface of the present invention can exhibit excellent performance such as compatibility, impact resistance, coatability (appropriately low viscosity), weather resistance, adhesion, etc., a wind power generator blade In addition to the paint for forming a coating on the surface of the substrate, for example, exterior paints and interior paints for vehicles (vehicles, ships, aircrafts, spacecrafts, etc.), protective paints such as power transmission lines and cables, or gas, liquid, slurry, etc. It is useful for various applications such as a paint for forming a surface coating film that comes into contact with the fluid.

[Method of manufacturing wind power generator blade]
Next, the manufacturing method of the blade of the wind power generator of this invention is demonstrated below.

  The method for producing a wind power generator blade of the present invention is to apply the substrate surface coating film-forming coating composition to the blade substrate surface to form a coating layer, and then to contain the solvent (G) contained in the coating layer Is a method of forming a coating film.

  The method for applying the coating composition is not particularly limited, and examples thereof include a method using a brush, a roller, a spray, a flow coater, an applicator and the like.

  The coating amount of the coating composition on the blade substrate surface may be appropriately set according to the intended dry film thickness, and is not particularly limited.

  A coating film is formed by removing the solvent (G) contained in the coating layer from the coating layer formed by coating the coating composition on the blade substrate surface. As the solvent (G) is removed from the coating layer, the contact efficiency between the hydroxyl group in the main agent (E) and the isocyanate group in the curing agent (F) increases, and the crosslinking reaction easily proceeds.

  The method for removing / recovering the solvent (G) is not particularly limited, for example, heat drying, reduced pressure drying, hot air drying and the like.

  The solvent (G) is preferably recovered and reused for environmental protection and cost reduction.

  The temperature at which the solvent (G) is removed varies depending on the type of solvent used, but may be any temperature that does not adversely affect the quality of the coating composition, and is usually from room temperature to 100 ° C, preferably from room temperature to 80 ° C is more preferred. If the temperature is within such a range, the solvent (G) is sufficiently removed, so that no foam marks are formed on the resulting coating film, and the curing reaction with the curing agent (F) is easy to proceed.

  In the present invention, the thickness of the coating film formed by removing the solvent (G) is preferably in the range of 20 to 300 μm, more preferably in the range of 20 to 150 μm, and still more preferably in the range of 20 to 100 μm. It is.

  As the blade base, a blade base usually used in a wind power generator can be adopted, and examples thereof include a blade base in which the surface of a wing-like plate piece made of wood is reinforced with fiber reinforced plastic (FRP).

  The blade substrate is not particularly limited, and is manufactured by a hand lay-up method using a polyester resin, a vacuum impregnation method using an epoxy resin, or the like.

  The shape and size of the blade base are not particularly limited.

  According to the method of manufacturing a blade of a wind power generator of the present invention, a wind turbine in which a coating film that is excellent in weather resistance and has excellent followability and adhesion to the blade base is formed on the surface of the blade base. Generator blades can be obtained.

  In addition, since the coating film formed on the blade substrate surface obtained by the production method of the present invention is excellent in flexibility, for example, the coating film can be subjected to a strong impact from raindrops, ice and snow, garbage, insects, birds, etc. Hard to get scratched. Moreover, the said coating film has performance, such as the outstanding weather resistance and stain resistance.

  The present invention will be described more specifically with reference to examples and comparative examples. However, the scope of the present invention is not limited to these examples.

  In the present invention, “%” means “% by mass” and “parts” means “parts by mass” unless otherwise specified.

  The measurement method and evaluation method used in the present invention are as follows.

[Measurement method of hydroxyl value]
The operating method was implemented according to JIS K1557-1 (2007) A method. However, a potassium hydroxide standard solution was used for titration.

[Method of measuring the number average molecular weight (Mn) of the polyether ester polyol (B)]
The Mn of the polyether ester polyol (B) in the present invention is a value measured under the following measurement conditions by a gel permeation chromatography method (GPC method) using standard polystyrene as a molecular weight standard. .
Measuring device: High-speed GPC device (“HLC-8220GPC” manufactured by Tosoh Corporation)
Column: The following columns manufactured by Tosoh Corporation were connected in series.
"TSKgel G5000" (7.8 mm ID x 30 cm) x 1 "TSKgel G4000" (7.8 mm ID x 30 cm) x 1 "TSKgel G3000" (7.8 mm ID x 30 cm) x 1 Book “TSKgel G2000” (7.8 mm ID × 30 cm) × 1 Detector: RI (differential refractometer)
Column temperature: 40 ° C
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 mL / min Injection volume: 100 μL (tetrahydrofuran solution with a sample concentration of 0.4 mass%)
Standard sample: A calibration curve was prepared using standard polystyrene.

[Method for measuring viscosity of modifier (D) and criteria for determination]
The viscosity of the modifier (D) containing the polyether ester polyol (B) and the polyfunctional polyether polyol (C) was measured according to the following conditions and judged according to the following criteria.
Measuring instrument: Cone plate viscometer (MST Engineering Co., Ltd.) Model: CV-1S
Measurement temperature: 30 ° C
Criteria for determining the viscosity of modifiers.
A: When less than 1000 mPa · s.
○: 1000 to 2000 mPa · s.
×: When exceeding 2000 mPa · s.

[Compatibility Evaluation Method and Criteria]
In a container, a fluoropolymer (A) and a modifier (D) [polyether ester polyol (containing B (E) and polyfunctional polyether polyol (C)] are mixed at a predetermined mass ratio. Then, a mixed solution (main agent (E)) is prepared.
Next, the mixture (main agent (E)) was allowed to stand at room temperature for 24 hours, and then the appearance was visually observed to determine compatibility according to the following criteria.
Criteria for compatibility.
○: Excellent compatibility when not separated.
X: When separated, the compatibility is poor.

[Impact resistance evaluation method and criteria]
The coating film was subjected to an impact resistance test in accordance with JIS K 5600-5-3 (2009) (weight drop resistance test) and evaluated according to the following criteria.
Weight drop: DuPont weight Weight: 300g
Shooting type: 1/8 inch, 1/4 inch Height: 30 cm, 40 cm
Criteria for impact resistance.
○: Excellent impact resistance when there is no change in the appearance of the coating film.
X: When a crack and peeling arise in a coating film, it is inferior to impact resistance.

(Measurement of water contact angle)
Kyowa Interface Science Co., Ltd., Model: Using Drop Master 700, measure the angle (water contact angle) between the tangent of ion-exchanged water 2 μl and the surface of the sample (coating film) to prevent ice adhesion according to the following criteria. Judged.
Criteria for anti-icing properties.
○: If it is 90 ° or more, the anti-icing performance is excellent.
X: If it is less than 90 °, it is inferior in anti-icing performance.

[Example 1]
In a reaction vessel, 472 parts of dipropylene glycol (hereinafter abbreviated as “DPG”), 528 parts of sebacic acid (hereinafter abbreviated as “Seb”), and 0.03 part of tetraisopropyl titanate (hereinafter abbreviated as “TiPT”). The mixture was stirred, mixed, and reacted at an internal temperature of 220 ° C. for 18 hours to obtain a bifunctional polyetherester polyol (B1) (hydroxyl value 112, Mn1000, liquid at room temperature).
To 45 parts of the above polyether ester polyol (B1), 25 parts of “Excenol 385SO” (trademark, manufactured by Asahi Glass Co., Ltd., polypropylene glycol, hydroxyl value 385) is added as a polyfunctional polyether polyol (C1) and stirred at room temperature. By mixing, a modifier (D1) (viscosity 1680 mPa · s / 30 ° C., colorless transparent liquid) was obtained.
Next, 46 parts of “Zeffle GK-570” (trademark, manufactured by Daikin Corporation, butyl acetate solution having a hydroxyl value of 55 to 65% and a nonvolatile content of 65% by mass), which is a fluororesin (A1), was added to the modifier (D1 ) 70 parts were added and mixed to obtain the main agent (E1).
The evaluation results of the main agent (E1) are shown in Table 1.
The main agent (E1) maintained a transparent state without separation even after being left for 24 hours, and was excellent in compatibility.
Next, after adding 100 ppm of dioctyltin diurarate as a curing catalyst to the main agent (E1), immediately after the addition of “TORONATE IDT70B” (trademark, manufactured by Perstorp, polyisocyanate curing agent, isophorone diisocyanate as a curing agent (F1) Trimer (hereinafter abbreviated as “IPDI trimer”), a butyl acetate solution having a nonvolatile content of 70% by mass, an isocyanate equivalent (hereinafter “NCO equivalent”) of the curing agent (F1) and a hydroxyl equivalent (hereinafter “OH”) of the main agent (E1). Equivalent ") (i.e., [NCO / OH equivalent ratio]) at a ratio of 1.02 equivalent, stirred for 2 minutes, and mixed to form the coating composition for forming a substrate surface coating film (P1) of the present invention. )
Immediately, the coating composition (P1) was applied onto the surface of the aluminum plate so that the film thickness after drying was 160 μm to form a coating layer, which was then heated in a dryer at 80 ° C. for 30 minutes to remove the solvent (acetic acid (Butyl) was removed, followed by curing at room temperature for 1 week to obtain a test plate (S1).
The test plate (S1) was subjected to a DuPont impact test, and the evaluation results are shown in Table 1.
The test plate (S1) was excellent in impact resistance without cracking or peeling of the coating film under all measurement conditions. The test plate (S1) was excellent in anti-icing property.

[Example 2]
A reaction vessel was charged with 497 parts of DPG, 503 parts of Seb, and 0.03 part of TiPT, stirred and mixed, and reacted at an internal temperature of 220 ° C. for 18 hours to produce a bifunctional polyetherester polyol (B2). (Hydroxyl value 150, Mn750, liquid at room temperature) was obtained.
To 45 parts of the above polyether ester polyol (B2), 25 parts of “Excenol 385SO” is added as a polyfunctional polyether polyol (C1), and the mixture is stirred and mixed at room temperature to obtain a modifier (D2) (viscosity 1450 mPa · s). / 30 ° C., colorless and transparent liquid).
Next, 70 parts of the modifying agent (D2) was added to 46 parts of “Zeffle GK-570” (a butyl acetate solution having a nonvolatile content of 65% by mass), which is a fluororesin (A1), and the main agent (E2) was mixed. Obtained.
The evaluation results of the main agent (E2) are shown in Table 1.
The main agent (E2) maintained a transparent state without separation even after being left for 24 hours, and was excellent in compatibility.
Next, after adding 100 ppm of dioctyltin diurarate as a curing catalyst to the main agent (E2), immediately after adding “TORONATE IDT70B” (trademark, manufactured by Perstorp, polyisocyanate curing agent, IPDI trimer, non-volatile) as curing agent (F1) 70 mass% butyl acetate solution) is blended at a ratio of 1.02 equivalent ratio of NCO equivalent of curing agent (F1) to OH equivalent of main agent (E2) (ie [NCO / OH equivalent ratio]). The mixture was stirred for 2 minutes and mixed to obtain a coating composition (P2) for forming a substrate surface coating film of the present invention.
Immediately in the same manner as in Example 1, a test plate (S2) was prepared using the coating composition (P2).
The test plate (S2) was subjected to a DuPont impact test, and the evaluation results are shown in Table 1.
The test plate (S2) was excellent in impact resistance, with no cracking or peeling of the coating film observed under all measurement conditions. The test plate (S2) was excellent in anti-icing property.

Example 3
In a reaction vessel, 35 parts of the polyether ester polyol (B2) obtained in Example 2, 15 parts of “Excenol 385SO” as the polyfunctional polyether polyol (C1), and PTMG650 (manufactured by Mitsubishi Chemical Corporation) as (C2) Polytetramethylene glycol, hydroxyl value 173) was added, and the mixture was stirred and mixed at room temperature to obtain a modifier (D3) (viscosity 1050 mPa · s / 30 ° C., colorless transparent liquid).
Next, 70 parts of the modifier (D3) was added to and mixed with 46 parts of “Zeffle GK-570” (a butyl acetate solution having a nonvolatile content of 65% by mass), which is a fluororesin (A1). Obtained.
The evaluation results of the main agent (E3) are shown in Table 1.
The main agent (E3) maintained a transparent state without separation even after being left for 24 hours, and was excellent in compatibility.
Next, after adding 100 ppm of dioctyltin diurarate as a curing catalyst to the main agent (E3), immediately after adding “TORONATE IDT70B” as a curing agent (F1) (trademark, manufactured by Perstorp, polyisocyanate curing agent, IPDI trimer, non-volatile 70 mass% butyl acetate solution) is blended at a ratio of 1.02 equivalent ratio of NCO equivalent of curing agent (F1) to OH equivalent of main agent (E3) (ie [NCO / OH equivalent ratio]). Then, the mixture was stirred for 2 minutes and mixed to obtain a coating composition (P3) for forming a substrate surface coating film of the present invention.
Immediately in the same manner as in Example 1, a test plate (S3) was produced using the coating composition (P3).
The test plate (S3) was subjected to a DuPont impact test, and the evaluation results are shown in Table 1.
The test plate (S3) was excellent in impact resistance with no cracking or peeling of the coating film observed under all measurement conditions. The test plate (S3) was excellent in anti-icing property.

Example 4
In a reaction vessel, 25 parts of the polyether ester polyol (B2) obtained in Example 2, 15 parts of “Exenol 385SO” as the polyfunctional polyether polyol (C1), 20 parts of PTMG650 as (C2), and ( As C3), 10 parts of “Excenol 430” (trademark, manufactured by Asahi Glass Co., Ltd., polypropylene glycol, hydroxyl value 42) was added and stirred and mixed at room temperature to obtain a modifier (D4) (viscosity 1190 mPa · s / 30 ° C., A colorless transparent liquid) was obtained.
Next, 70 parts of a modifier (D4) was added to 46 parts of “Zeffle GK-570” (a butyl acetate solution having a nonvolatile content of 65% by mass), which is a fluororesin (A1), and mixed to obtain the main agent (E4). Obtained.
The evaluation results of the main agent (E4) are shown in Table 1.
The main agent (E4) maintained a transparent state without separation even after being left for 24 hours, and was excellent in compatibility.
Next, after adding 100 ppm of dioctyltin diurarate as a curing catalyst to the main agent (E4), immediately after the addition of “TORONATE IDT70B” as a curing agent (F1) (trademark, manufactured by Perstorp, polyisocyanate curing agent, IPDI trimer, non-volatile 70 mass% butyl acetate solution) is blended at a ratio of 1.02 equivalent ratio of NCO equivalent of curing agent (F1) to OH equivalent of main agent (E4) (ie [NCO / OH equivalent ratio]). The mixture was stirred for 2 minutes and mixed to obtain a coating composition (P4) for forming a substrate surface coating film of the present invention.
Immediately in the same manner as in Example 1, a test plate (S4) was produced using the coating composition (P4).
The test plate (S4) was subjected to a DuPont impact test, and the evaluation results are shown in Table 1.
The test plate (S4) was excellent in impact resistance without cracking or peeling of the coating film under all measurement conditions. The test plate (S4) was excellent in anti-icing property.

[Comparative Example 1]
It carried out by the same operation as Example 1 using the main ingredient (E5) which consists only of a fluoropolymer (A1), without mixing the modifier (D1) used in Example 1. FIG.
After adding 100 ppm of “Zeffle GK-570” (a butyl acetate solution having a nonvolatile content of 65% by mass) as a fluororesin (A1) which is the main agent (E5) and 100 ppm of dioctyltin dilaurate which is a curing catalyst to the reaction vessel, Immediately, “TORONATE IDT70B” (trademark, manufactured by Perstorp, IPDI trimer, butyl acetate solution having a nonvolatile content of 70% by mass) as a curing agent (F1), an NCO equivalent of the curing agent (F1) and an OH of the main agent (E5) It was blended at a ratio of 1.02 equivalent to the equivalent (ie, [NCO / OH equivalent ratio]), stirred for 2 minutes and mixed to obtain a coating composition (P5) for forming a substrate surface coating film.
Immediately, the coating composition (P5) was applied onto the surface of the aluminum plate so that the film thickness after drying was 160 μm to form a coating layer, which was then heated in a dryer at 80 ° C. for 30 minutes to give a solvent (acetic acid (Butyl) was removed, followed by curing at room temperature for 1 week to obtain a test plate (S5).
The test plate (S5) was subjected to a DuPont impact test, and the evaluation results are shown in Table 2.
As a result of the impact resistance test, the test plate (S5) was cracked in the coating film, peeled off from the substrate, and was inferior in impact resistance. Further, the test plate (S5) had good anti-icing property.

[Comparative Example 2]
Instead of the modifier (D1) used in Example 1, “Nipporan 800” (trademark, manufactured by Nippon Polyurethane Industry Co., Ltd., average hydroxyl group number 4, hydroxyl group, which is a polyfunctional polyester polyol as the modifier (D6) The same operation as in Example 1 was performed using a valence of 290, a number average molecular weight of 700, and a viscosity of 230,000 mPa · s / 30 ° C.
In a reaction vessel, 46 parts of “Zeffle GK-570” (a butyl acetate solution having a nonvolatile content of 65% by mass) as the fluorine-containing resin (A1) and “Nipporan 800, which is a polyfunctional polyester polyol as the modifier (D6)”. Was added and stirred for 2 minutes to obtain a coating composition (P6).
The coating composition (P6) was cloudy and separated into two phases after standing for 24 hours, so the compatibility was poor.

[Comparative Example 3]
In a reaction vessel, 501 parts of diethylene glycol (hereinafter abbreviated as “DEG”), 117 parts of trimethylolpropane (hereinafter abbreviated as “TMP”), 503 parts of adipic acid (hereinafter abbreviated as “AA”), and 0.03 part of TiPT was added, stirred and mixed, and reacted at an internal temperature of 220 ° C. for 18 hours to obtain a polyfunctional polyetherester polyol (hydroxyl value 180, liquid at normal temperature). The polyfunctional polyether ester polyol obtained above is referred to as a modifier (D7).
The main component (E7) was obtained by adding 46 parts of “Zeffle GK-570” as the fluororesin (A1) to 70 parts of the polyfunctional polyether ester polyol which is the modifier (D7) obtained above and mixing. .
The coating composition (P7) obtained by blending the main agent (E7) was cloudy and separated into two phases after standing for 24 hours, so the compatibility was poor.
A test plate (S7) was produced using the coating composition (P7) in the same manner as in Example 1.
The test plate (S7) was subjected to a DuPont impact test, and the evaluation results are shown in Table 2.
The coating composition (P7) was cloudy and separated into two phases after standing for 24 hours, so the compatibility was poor.

In addition, the symbol in Table 1 and Table 2 means the following name.
DPG: dipropylene glycol Seb: sebacic acid TiPT: tetraisopropyl titanate PPG: polypropylene glycol IPDI trimer: trimer of isophorone diisocyanate (trimer)
DEG: Diethylene glycol TMP: Trimethylolpropane AA: Adipic acid

  The coating composition for forming a substrate surface coating film of the present invention can exhibit excellent performance such as coating property (appropriately low viscosity), compatibility, impact resistance, anti-icing property, etc. Coating material for coating the surface of blades of automobiles, exterior paints and interior paints for electronic devices such as smartphones and vehicles (vehicles, ships, aircrafts, spacecrafts, etc.), protective paints for power transmission lines and cables, or gases and liquids It is useful for various applications such as a coating for forming a coating film on a substrate surface that comes into contact with a fluid such as a slurry. In addition, the method for producing a blade of a wind power generator according to the present invention can form a strong coating film on which the coating composition is difficult to peel off on the surface of the substrate of the blade, and thus can exhibit excellent impact resistance.

Claims (10)

A fluorine-containing polymer (A) having a hydroxyl value in terms of solid content of 15 to 110 mgKOH / g, a polyetherester polyol (B) having a number average molecular weight of 500 to 3000, and a polyfunctional polyether polyol (C) A coating composition for forming a coating film on a substrate surface, which is obtained by blending a main agent (E) obtained by mixing a modifier (D), a curing agent (F), and a solvent (G). 2. The coating composition for forming a coating film on a substrate surface according to claim 1, wherein the polyether ester polyol (B) is synthesized from dipropylene glycol and an aliphatic dicarboxylic acid as raw materials. The coating composition for forming a substrate surface coating film according to claim 1, wherein the curing agent (F) is a polyisocyanate curing agent. Content of the said hardening | curing agent (F) is 40-120 with respect to a total of 100 mass parts of the said fluoropolymer (A), polyetherester polyol (B), and polyfunctional type polyether polyol (C). The coating composition for forming a coating film on a substrate surface according to claim 1, wherein the coating composition is in the range of part by mass. The mass ratio [A / (B + C)] of the fluoropolymer (A) to the total mass of the polyether ester polyol (B) and the polyfunctional polyether polyol (C) is in the range of 10/90 to 90/10. The coating composition for forming a coating film on a substrate surface according to claim 1. The isocyanate group of the said hardening | curing agent (F) is 0.5-3 with respect to 1 mol of hydroxyl groups which the said fluoropolymer (A), polyether ester polyol (B), and polyfunctional polyether polyol (C) have. The coating composition for forming a coating film on a substrate surface according to claim 1, which is obtained by blending in a range of 0.0 mol. The polyfunctional polyether polyol (C) is contained in a range of 10 to 600 parts by mass with respect to a total of 100 parts by mass of the polyether ester polyol (B) and the polyfunctional polyether polyol (C). 1. The coating composition for forming a substrate surface coating film according to 1. 2. The coating composition for forming a coating film on a substrate surface according to claim 1, which is used for forming a coating film on the surface of a blade substrate. 2. The coating composition for forming a coating film on a substrate surface according to claim 1, wherein the coating composition is used for forming a coating film on the surface of a blade substrate that contacts at least one fluid selected from gas, liquid, and slurry. The substrate surface coating film forming coating composition according to any one of claims 1 to 9 is applied to the blade substrate surface to form a coating layer, and then the solvent (G) contained in the coating layer is added. A method for producing a blade of a wind power generator, comprising removing and forming a coating film.